外型和内型C-2位单取代降冰片烯衍生物的核磁共振波谱研究
收稿日期: 2020-12-28
网络出版日期: 2021-03-12
基金资助
国家自然科学基金资助项目(51873054);国家级大学生创新训练计划资助项目(201910359037)
NMR Spectroscopic Studies on (exo, endo) C-2 Monosubstituted Norbornene Derivatives
Received date: 2020-12-28
Online published: 2021-03-12
C-2位单取代降冰片烯衍生物中降冰片烯环存在各向异性，且多数为外型和内型异构体的混合物，导致其结构解析困难.针对这一问题，本文在制备了单一构型的C-2位羧基和羟甲基取代的降冰片烯衍生物的基础上，利用1H NMR、DEPT135、1H-1H COSY、1H-13C HMQC、1H-1H NOESY谱和相应的耦合裂分信息，对外型-5-降冰片烯-2-羧酸、内型-5-降冰片烯-2-羧酸、外型-5-降冰片烯-2-甲醇和内型-5-降冰片烯-2-甲醇的1H和13C NMR信号进行归属，并探讨了降冰片烯衍生物的取代基种类及空间构型对1H NMR化学位移的影响.
关键词： 5-降冰片烯-2-羧酸; 5-降冰片烯-2-甲醇; 构型异构体; 核磁共振(NMR); 结构归属
王子豪 , 徐赫 , 汪涛 , 杨善中 , 丁运生 , 魏海兵 . 外型和内型C-2位单取代降冰片烯衍生物的核磁共振波谱研究[J]. 波谱学杂志, 2021 , 38(3) : 323 -335 . DOI: 10.11938/cjmr20202880
The 1H NMR spectra of C-2 monosubstituted norbornene and its derivatives are usually difficult to assign due to the anisotropy effect of norbornene ring and being a mixture of exo- and endo- isomers. Based on the preparation of configurationally pure C-2 substituted norbornene derivatives, this study assigned the 1H and 13C NMR signals of exo-5-norbornene-2-carboxylic acid, endo-5-norbornene-2-carboxylic acid, exo-5-norbornene-2-methanol and endo-5-norbornene-2-methanol by combined use of 1H NMR, DEPT135, 1H-1H COSY, 1H-13C HMQC and 1H-1H NOESY spectroscopy, and corresponding coupling constants. The effects of norbornene derivatives' C-2 substituents and their configurations on 1H NMR chemical shifts of the compunds were also investigated.
| 1 | SCHLEYER P V R , WILLIAMS J E , BLANCHARD K R . Evaluation of strain in hydrocarbons. The strain in adamantane and its origin[J]. J Am Chem Soc, 1970, 92 (8): 2377- 2386. |
| 2 | KOVA?I? S , SLUGOVC C . Ring-opening metathesis polymerisation derived poly(dicyclopentadiene) based materials[J]. Mater Chem Front, 2020, 4 (8): 2235- 2255. |
| 3 | FERNANDEZ I , BICKELHAUPT F M . Origin of the "Endo Rule" in Diels-Alder reactions[J]. J Comput Chem, 2014, 35 (5): 371- 376. |
| 4 | RULE J D , MOORE J S . ROMP reactivity of endo- and exo-dicyclopentadiene[J]. Macromolecules, 2002, 35 (21): 7878- 7882. |
| 5 | KOICHIRO N , MASAO N . The Synthesis and absolute configuration of optically active tricyclo[4.3.0.03, 8] nonane (Twist-brendane)[J]. Bull Chem Soc Jpn, 1973, 46 (3): 888- 892. |
| 6 | JANSSEN A J M , KLUNDER A J H , ZWANENBURG B . Enzymatic resolution of norbor(NE)nylmethanols in organic media and an application to the synthesis of (+)- and (?)-endo-norbornene lactone[J]. Tetrahedron, 1991, 47 (29): 5513- 5538. |
| 7 | ZHANG H K , CHAN W H , LEE A W M , et al. Synthesis of chiral sultams and their application as chiral auxiliaries in an asymmetric Diels-Alder reaction[J]. Tetrahedron-Asymmetr, 2005, 16 (4): 761- 771. |
| 8 | CAMPAGNA M , TRZOSS M , BIENZ S . More than a protective group: ? Synthesis and applications of a new chiral silane[J]. Org Lett, 2007, 9 (19): 3793- 3796. |
| 9 | KANAO M , OTAKE A , TSUCHIYA K , et al. Stereo-selective synthesis of exo-norbornene derivatives for resist materials[J]. J Photopolym Sci Tech, 2009, 22 (3): 365- 370. |
| 10 | KANAO M , OTAKE A , TSUCHIYA K , et al. Stereo-selective synthesis of 5-Norbornene-2-exo-carboxylic scid-rapid isomerization and kinetically selectivehydrolysis[J]. Int J Org Chem, 2012, 2 (1): 26- 30. |
| 11 | DOU M , ZHAO Q , HOU X L , et al. Structural assignment and quantitative analysis for hydrogenation products of anthracene by NMR technology[J]. Chinese J Magn Reson, 2020, |
| 11 | 窦梦, 赵奇, 侯相林, 等. 蒽加氢产物的结构指认和定量核磁共振分析[J]. 波谱学杂志, 2020, 10 |
| 12 | HORST F. Basic one- and two-dimensional NMR spectroscopy(5th ed.)[M]. New York, 2010. |
| 13 | YIN T P , WANG Z , CHEN Y , et al. An NMR analysis of 10-indol cytochalasin chaetoglobosin F[J]. Chinese J Magn Reson, 2019, 36 (1): 74- 82. |
| 13 | 尹田鹏, 汪泽, 陈阳, 等. 10-吲哚细胞松弛素chaetoglobosin F的NMR解析[J]. 波谱学杂志, 2019, 36 (1): 74- 82. |
| 14 | KARPLUS M . Vicinal proton coupling in nuclear magnetic resonance[J]. J Am Chem Soc, 1963, 85 (18): 2870- 2871. |
| 15 | 薛松. 有机结构分析[M]. 合肥: 中国科学技术大学出版社, 2005. |
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